Thermoset epoxy resin plasticized with a glycol ether-ester



United States Patent 3,073,793 THERMOSET EPOXY RESIN PLASTICIZED WITH A GLYCOL ETHER-ESTER Frank P. Greenspan, Larchmont, and Rupert E. Light, ha, Poughkeepsie, N.Y., assignors to FMC Corporation, a corporation of Delaware No Drawing. Filed June 30, 1959, Ser. No. 823,848

Claims. (Cl. 260-314) found widespread use in the manufacture of coatings, in

the encapsulation of electrical components, and in the manufacture of laminates andadhesives. They suffer a basic disadvantage, however. By reason of their molecular structures, in thermoset condition they are rigid and are inclined toward brittleness. External plasticizers of the type commonly used with thermoplastic resins, e.g. the oil plasticizers normally employed for example with vinyl resins and cellulosic resins, generally have been found unsuited for use with these complex epoxy resins. This unsuitability is common to thermoset resins, and manifests itself in exudation of the plasticizer from the thermoset resin on ageing and in generally poor plasticizer efficiency. As a result, in order to flexibilize thermoset resinuous compositions derived from complex epoxy resins, users have found it necessary to modify the resins chemically before their conversion to a thermoset condition, by reaction with secondary polymer materials e.g. polyamides, Thiokol synthetic rubbers and other polymers containing functional groups reactive with the resins. Reaction of these secondary polymers with the complex epoxy resins complicates use of the resins and further introduces substantial chemical changes in the backbone structure of the resins, which in many instances is undesirable.

It is a feature of this invention to provide plasticized, thermoset resinous products derived from complex epoxy resins and curing agents therefor, and a method of providing plasticity in these resinous products with external plasticizers which are substantially non-reactive with the epoxy resins.

It is a further feature of this invention to provide such plasticized, thermoset resinous compositions wherein the external plasticizer is efiicient and is resistant to exudation.

In accordance with the present invention a complex epoxy'resin containing oxiraneoxygen on terminal alkoxy groups only, is blended with up to about 40% of the total of a glycolether ester having a molecular weight of about 258 to 450 to produce a thermoplastic composition, and

- epoxy resins, the

resin. Apparently, the

"ice

ene glycol. Their structures are represented by the fol-,

lowing formula:

wherein R is an aliphatic, aryl or aralkyl group and 11:1 or 2.

Various ethylene glycol-ethers are available commercially under the trade name Cellosolve. Diethylene glycol-ethers are available under trade name Carbitol.

The acids and anhydrides useful in forming the ester plasticizer are the monobasic saturated and unsaturated aliphatic acids and their anhydrides. The esterifying acid must be chosen to provide an ester which has a low vapor pressure at operating temperatures to which the plasticized compositions will be subjected. Proper choice of esterifying acid is based on the combined molecular Weights of the esterifying acid, the group which forms the ether with the glycol, and the glycol residue. The formula of the ester plasticizer may be represented as H H n(o-c-o-)ooon' H H n where n =l to 2, R is ether forming radical, and R is the ester forming radical.

The molecular weight of the ester should equal at least 258 in order that the plasticizer will be SlllfiClfiIlilY nonvolatile to resist exudation" from the resinous composition either before, during or subsequent to its cure. Accordingly, the ester and ether radicals may be chosen in any ratio provided the glycol residue plus these radicals have a combined molecular weight of at least 258. An example of an ester having a suitable molecular weight is methyl Cellosolve oleate wherein the glycol residue has a molecular weight of 44, the methyl group, that is the ether radical, has a molecular weight of 15 and the oleate group, that is the ester radical, a molecular weight of 281, which combines to give a molecular weight of 340.

It has been found that esters having molecular weights substantially below about 258 'are unsuitable for general use as plasticizers for epoxy resins which are to be subjected to elevated temperatures in the processing or curing of the resins or in subsequent use of the thermo-set volatilities of esters having molecular weights substantially below 258 cause them to be lost from the resin either during cure or in use of the cured product when the resin or the product is exposed;

to elevated temperatures. Whatever the explanation may be as to the unsuitability of the esters having molecular weights below 258, as plasticizers for general use for fact appears to be that when epoxy resins are required to encounter elevated temperatures, either in curingof the resin or in use'of the thermo-set resinous product, loss of the plasticizer does not occur or become manifest when the plasticizer is an ester having a molecular weight of 258 or more, in accordance with the epoxy resin component in the resulting blend is crosslinked with a curing agent for the epoxy resin. The plas ticized, thermoset resinous product which results has a high degree of resiliency and toughness, and is resistant to impact. Furthermore, it retains these desirable properties on ageing, even when the resinous product is exposed to elevated temperatures during its formation or use.

The plasticizers useful herein are formed by the esterification of glycol-ethers with aliphatic acids or anhydrides. The glycol-ethers linkages, and are the ethers of ethylene'glycol or diethylcontain both alcohol groups and ether the present invention. As regards an upper limit on the molecular weight of the ester, it has been determined that esters having molecular weights substantiallyhigher than 450 are difficult to compound with the resin by reason of their high melting points. A

The esters are formed according to well-known esterification techniques. Typically, the acid and the glycol other may be reacted in the presence of an acid such as sulfuric acid, which functions as a catalyst. The glycol-ether esters have physical properties ranging from pourable liquids to soft solids. Typical liquid glycol-ether esters are ethyleneglycol methylether oleate, ethyleneglycol, ethylether ricinoleate, ethyleneglycol ethylether stearate, and .diethyleneglycol ethylether riciinoleate. Typical useful glycol-ether esters which are solids at or about room temperature are dicthyleneglycol ethylether laurate and diethyleneglycol ethylether stearate. Choice of a liquid or solid plasticizer will be made on the basis of desired handling characteristics.

Thermoplastic complex epoxy resins which are useful herein are the di-(epoxyalkyl) ethers of polyhydric phenols. -These resins, which are readily available under the trade names Epon resins and Araldite resins, are produced by condensation of polyhydric phenols with halopoxyalkanes or dichlorohydrins in the presence of alkali, or with polyepoxides. They contain epoxy and in some cases also hydroxy radicals on terminal alkoxy groups in the resin, and containinternal hydroxy groups and ether linkages. Polyhydric phenols which are useful in forming the resins are exemplified by the bisphenols, that is the dihydroxy diphenyl alkanes, resorcinol, hydroquinone, and the phenolaldehyde condensates. Suitable haloepoxyalkanes include epichlorohydrin, that is l-chloro-2,3- epoxypropane, l-chloro-2,3-epoxypentane and the like while suitable dichlorohydrins include glycerol dichlorohydrin and other similar compounds which convert to the corresponding epoxy compounds in the presence of alkali.

Typical polyepoxy compounds useful in forming the resins are butane dioxide and hexane dioxide.

The term epoxy oxygen on terminal alkoxy groups of the resin only is intended to signify epoxy groups attached to ether alkoxy groups which are at the ends of the resin molecule. This would include 1,2- positioned epoxy groups such as exist in epichlorohydrin-bisphenol epoxy resins as well as epoxy groups attached to the terminal alkoxy groups in other positions, for example 2,3-positioned epoxy groups in epoxy resins formed from 1- chloro-2,3-epoxypentane by reaction with polyhydric phenols.

Resins having more than one and less than two epoxy groups per molecule are' particularly useful herein, and are formed by reaction of a stoichiometric excess of the epoxy containing ingredient, e.g. epihalohydrin or polyepoxide, with the polyhydric phenol. However, in some cases the epoxy groups ring open to provide a resin having less than one epoxy group per molecule, and these resins can be plasticized with the present glycol-ether ester plasticizers.

Reaction products of bisphenols with an excess of epichlorohydrin, formed in the presence of an alkali, are the common complex epoxy resins and are preferred for use in forming the present plasticized compositions. These resins in common with the class of complex epoxy resins as a whole are available in liquid or solid state, and are soluble'in'organic solvents such as ketones and alcohols. They can be blended with the herein liquid or solid plasticizers simply by stirring them with the plasticizer, by mixing them with the plasticizer in a mutual solvent, or by heating the resin and/or plasticizer to their respective melting points and stirring them together. Choice of a suitable mixing method will be made on the basis of the properties of the resin and plasticizer.

'Th'e plasticizer normally is employed in the thermoset resinous product in an amount of no more than 40 parts by Weight per 60 parts by weight of the epoxy resin. The exact amount employed is determined by the degree of plasticization desired, and may be as little as only a few percent in cases where it is desired merely to eliminate the extreme brittleness of the thermoset product. Use of amounts of plasticizer in excess of 40% is not recommended as at higher plasticizer levels the plasticizing efficiency falls off, and physical properties of the resin are deletcriously affected.

The complex epoxy resin component of the resin-plasticizer mixture is cured with a suitable curing agent, in order to provide the present plasticized, thermoset resinous product. The curing agent is introduced into the resin preferably immediately prior to conversion of the resin to thermoset condition, although it can be introduced at any previous time if precautions are taken to avoid premature cure of the resin. Suitable curing agents are of having hardnesses of the two types. The first type is the class of poly-functional crosslinking agents which contain as functional groups primary or secondary amine groups, mercaptan groups, carboxyl groups and other active hydrogen containing groups which are capable of crosslinking with the epoxy resin. The second type is the class of catalytic agents members of which are exemplified by boron trifluoride and tertiary amines which activate the hydroxyl and epoxy groups on adjacent epoxy resin molecules, thereby making possible polyaddition between these activated groups to link the molecules together. The polyfunctional crosslinking agents normally are employed in the amount of about 5-15 calculated on the resin, although they may be employed in greater or lesser amounts depending on the extent and speed of cure and the end product properties desired. The amount of catalytic curing agent which is employed will depend on the agent used, and is determined largely on an empirical basis. Thus for example generally when boron trifluoride is used as a catalyst, about 1-4% of this reagent is used, whereas with tertiary amines generally 4 to 8% of catalyst is employed. Heating normally accelerates the curing reaction, although as is Well known certain of the curing agents for example certain amines or boron trifiuoride, will permit room temperature cure.

Other compounding agents, for example fillers, dyes, pigments, and modifying polymers such as polyamide resins, Thiokol synthetic rubbers and the like may be employed in the plasticized products as desired. These added compounding agents may be incorporated into the complex epoxy resin at any time prior to conversion of the resin to thermoset condition.

The thermoset resinous products formed by reaction of the complex epoxy resin with the curing agent and containing the glycol-ether esters as plasticizers, have prop erties which range from hard to soft, and from slightly brittle to flexible and resilient. At a plasticizer level of about 40 parts per 60 parts of resin, the thermoset resinous composition is quite rubbery and highly resilient. At a plasticizer level of 20 parts per parts of resin the thermoset product is hard, but is substantially less hard than a corresponding unplasticized product, having a hardness on the Barcol hardness scale in the neighborhood of 50 as compared with a hardness of approximately 80 in the case of the unplasticized product. Films of thermoset resinous product containing plasticizer in amounts falling within the above range are flexible, and show a high degree of resistance to cracking. Ageing does not reduce the effectiveness of the plasticizer, tests conducted 27 months after formation of the compositions above order. Use of lesser amounts of plasticizer results in production of thermoset products having correspondingly higher hardness values. This is desirable particularly in the case of films, where flexibility and resilience are of importance but the product must also have high hardness.

The plasticizer functions in the thermoset resinous product as an external plasticizer. That is to say, it acts as a mechanical plasticizing agent and does not become a part of the resin molecule. This is evidenced by the fact that a major portion of the plasticizer in unchanged form can be extracted from shavings of the thermoset resinous product, by refluxing for 10 to 15 hours with solvents such as heptane or ethyl ether. it is difficult to remove all of the plasticizer as it is bound mechanically within the intractable thermoset resin, and accordingly cannot be reached readily by the solvent.

A very important use of these plasticized, thermoset resinous products is as surface coatings. In this case the complex epoxy resin, a suitable curing agent and the plasticizer are dissolved or suspended in a solvent and are deposited therefrom onto the surface to be coated. The solvent then is evaporated to deposit a film which cures to a tough, resilient coating. The hardness and degree of resilience and flexibility in the film can be regulated readily by proper choice of glycol-ether ester plasticizer and amount thereof.

The resin-plasticizer blends likewise are useful in the production of castings. A liquid composition comprising a complex epoxy resin, a plasticizer and a curing agent is blended and poured into a mold, where it is cured either at room temperature or by the application of heat. The thermoset resinous product which results shows excellent reproduction of the mold shape, and unusual freedom from crazing and changes in physical properties on ageing. A particularly interesting application of casting resins of this type is in the encapsulation or potting of electrical components. Other uses of these compositions will suggest themselves to those versed in the polymer art.

The following examples are given by way of illustration only, and are not to be construed as limiting the ingredients, proportions thereof or reaction conditions which are within the scope of this invention.

EXAMPLE 1 Blank, DETA (Diethylene Triamine) Cure 50 gr. of Epon 834 was placed in an aluminum foil cup, and 4 gr. of DETA was stirred into it. The Epon 834 is a semi-solid epoxy resin having a melting point of 20-28 C., and an epoxide equivalency of 225-290, and is formed by reaction of 4,4-dihydroxydiphenyl propane and epichlorohydrin. A small portion of this mixture was applied as a 3 mil coating to a 3" x 6", 30 gauge tin plate and a further small portion was applied in the same way to a 3" x 6", 20 gauge steel plate. The coated plates and the aluminum foil cup containing the resin mixture were placed in an oven and baked at 115 C. for 30 minutes. The plates and cup then were removed from the oven and permitted to cool at room temperature. Following this, the aluminum foil cup was stripped from the cured sample contained therein, and this sample and the coated plates were aged for one week. The cured casting which was removed from the aluminum foil cup was tested at the end of this period for hardness with a Barcol impressor, and the film coating on the tin plate was tested for flex resistance by bending the tin plate rapidly over mandrels and noting the minimum diameter mandrel over which the plate could be bent without film cracking. This film also was tested for adhesion by scratching the film with a knife. The coating on the steel plate was tested for impact resistance in a falling weight Gardner impact tester. Results of these tests appear in Table I.

EXAMPLE 2 Plasticizer, DET A Cure 47.5 gr. of Epon 834, 2.5 gr. of ethyleneglycol methyl- 4 gr. of DETA were mixed, and treated See Table I ether stearate, and

according to the procedure in Example 1.

for results.

EXAMPLE 3 Plasticizer, DETA Cure gr. of Epon 834, 15 gr. of ethyleneglycol methylether stearate, and 4 gr. of DETA were mixed, and treated according to the procedure in Examples 1 and 2. See Table I for results.

The following table, Table II, records the properties of unplasticized and plasticized Epon 828 cured resins which were aged for periods up to 27 months. The Epon 828 is a viscous, liquid epoxy resin having a melting point of 8-12 C. and an epoxide equivalency of 190 to 210 and is formed by reaction of 4,4-dihydroxydiphenyl propane and epichlorohydrin in a molar ratio, respectively, of about 1:2. Each of the samples was prepared as a casting by the technique described above, that is the Epon resin, the plasticizer and the curing agent were mixed in an aluminum foil cup and cured therein. The percent and nature of plasticizer, the cure times and the curing temperatures'are given in the table. The curing agent employed in these examples was curing agent D, and this agent was used in the amount of 10.5 parts per parts of formulation. Curing agent D is the 2-ethylhexoic acid salt of tri-(dimethyl aminomethyl) phenol.

TABLE II Per- Curing, Curing, Aged, Barcol Plastlelzer cent Hrs. Temp., Months Hard- C. ness 8 ant; 0 2 120 22 83 Ethyleneglycol 1 butylether stearate 20 2 120 15 45 Ethyleneglycol butylether oleate 20 2 120 15 53 Ethyleneglycol butylether laurate 20 2 120 15 45 Ethyleneglycol methylether laurate 20 2 120 15 35-40 Ethyleneglycol methylether stearate 20 2 120 22 45 Ethyleneglycol methylether oleate 20 2 120 24 5255 Ethyleneglycol butylether soyoate 20 1. 5 27 60 Diethyleneglycol 2 ethylether oleate 20 1. 5 115 27 45-55 1 Butyl Cellosolve steal-ate. B Ethyl earbitol oleate.

Having described our invention, what we claim asnew and desire to secure by Letters Patent of the United States where R is a 1 to 4 carbon alkyl radical, R' -is a 2 to 17 carbon straight-chain aliphatic hydrocarbon group, and n is an integer from 1 to 2, said ester having a molecular weight of about 258 to 450 and being compatible with said thermoset resin and exhibiting its plasticizing effect on said thermoset resin on ageing of the thermoset resinous product.

2. Plasticized, thermoset resinuous product, consisting essentially of (a) a thermoset resin formed by reaction of a complex epoxy resin having epoxy oxygen attached to adjacent carbon atoms on terminal 3 to 6 carbon alkoxy groups of the resin only, with a curing agent for said epoxy resin, and (b) as an external plasticizer for the thermoset resin about 5 to 40 parts by weight of an ethylene glycol-ether ester of the following formula where R is a 1 to 4 carbon alkyl radical, R is a 2 to 17 carbon straight-chain aliphatic hydrocarbon group, and 11:1, said ester having a molecular weight of about 258 to'450 and being compatible with said thermoset resin and exhibiting its plasticizing effect on said thermoset resin on ageing of the thermoset resinous product.

butylether stearate said plasticizer being 3. Plasticized, thermoset resinous product, consisting essentially of (a) a thermoset resin formed by reaction of a complex epoxy resin having epoxy oxygen attached to adjacent carbon atoms on terminal 3 to'6 carbon alkoxy groups of the resin only, with a curing agent for said epoxy resin, and (b) as an external plasticizer for the thermoset resin'about to 40 parts-by weight of a diethylene glycolether 'ester of the following formula where R is a 1 to 4'carbon alkyl radical, R is a 2 to 17 carbon straight-chain aliphatic hydrocarbon group and n=2, said ester having a molecular weight of about 258 to 450 and being compatible with said thermoset resin and exhibiting its plasticizing effect on said thermoset resin on ageing of the thermoset resinous product.

4. Plasticized, thermoset resinous product, consisting essentially of (a) a thermoset resin formed by reaction of a curing agent with a complex epoxy resin having epoxy oxygen attached to adjacent carbon atoms on 3 to 6 carbon terminal alkoxy groups of the resin only, said epoxy resin being formed by reaction of a polyhydric phenol with an epihalohydrin, and (b) as an external plasticizer for the thermoset resin about 5 to 40 parts by weight of a glycolether ester of the following formula H H nocc)ooon H H n Where R is a l to 4 carbon alkyl radical, R is a 2 to 17 carbon straight-chain aliphatic hydrocarbon group and n is an integer from 1 to 2, said ester having a molecular weight of about 258 to 450 and being compatible with 7 said thermoset resin and exhibiting its plasticizing eifect on said thermoset resin on ageing of the thermoset resinous product.

5. Plasticized, thermoset resinous product, consisting essentially of (a) a thermoset resin formed by reaction of a' complex epoxy resin having epoxy oxygen attached to adjacent carbon atoms on terminal 3 to 6 carbon alkoxy groups of the resin only, with a curing agent for said epoxy resin, and (b) as an external plasticizer for the thermoset resin about 5 to 40 parts by weight of ethyleneglycol butylether oleate said plasticizer being compatible with said thermoset resin and exhibiting its plasticizing eifect on said thermoset resin on ageing of the thermoset resinous product.

6. Plasticized, thermoset resinous product, consisting essentially of (a) a thermoset resin formed by reaction of a complex epoxy resin having epoxy oxygen attached to adjacent carbon atoms on terminal 3 to 6 carbon alkoxy groups of the resin only, with a curing agent for said epoxy resin, and (b) as an external plasticizer for the thermoset resin about 5 to 40 parts by weight of ethylene-glycol compatible with said thermoset resin and exhibiting its plasticizing effect on said thermoset resin on ageing of the thermoset resinous product.

7. Plasticized, thermoset resinous product, consisting essentially of (a) a thermoset resin formed by reaction of a complex epoxy resin having epoxy oxygen attached to adjacent carbon atoms on terminal 3 to 6 carbon alkoxy groups of the resin only, with a curing agent for said epoxy resin, and (b) as an external plasticizer for the thermoset resin about 5 to 40 parts by weight of ethyleneglycol methylether laurate said plasticizer being compatible with said thermoset resin and exhibiting its plasticizing effect on said thermoset resin on ageing of the thermoset resinous product.

8. Plasticized, thermoset resinous product, consisting essentially of (a) a thermoset resin formed by reaction of a complex epoxy resin having epoxy oxygen attached to adjacent carbon atoms on terminal 3 to 6 carbon alkoxy groups of the resin only, with a curing agent for said epoxy resin, and (b) as an external plasticizer for the thermoset resin about 5 to 40 parts by weight of dicthylene-glycol ethylether oleate said plasticizer being compatible with said thermoset resin and exhibiting its plasticizing effect on said thermoset resin on ageing of the thermoset resinous product.

9. Thermosetting composition useful in forming a plasticized, theremoset resinous product, consisting essentially of in admixture (a) a complex epoxy resin having epoxy oxygen attached to adjacent carbon atoms on 3 to 6 carbon terminal alkoxy groups of the resin only, (2) a curing agent for said epoxy resin, and (c) about 5 to 40 parts of a glycol-ether ester of the following formula the thermoset resin about 5 to 40 parts by weight of a glycol-ether ester of the following formula where R is a 1 to 4 carbon alkyl radical, R is a 2 to 17 carbon straight-chain aliphatic hydrocarbon group and n is an integer from 1 to 2, said ester having a molecular weight of about 258 to 450 and being compatible with said theromet resin and exhibiting its plasticizing effect on said thermoset resin on ageing of the thermoset resinous product.

References Cited in the file of this patent UNITED STATES PATENTS 2,768,153 Shokal Oct. 23, 1956 2,801,229 De Hotf July 30, 1957 2,894,920 Ramos July 14, 1959 OTHER REFERENCES Modern Plastics Encyclopedia Issue, September 1954, pub. Plastics Catalogue Corp., Bristol, C0nn., page 818, Plasticizers Chart.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3,073,793 January 15, 1963 Frank Po Greenspan et ale It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2 line 10, after "under" insert the line after "is", first occurrence, insert the line 70 for "riciinoleate" read ricinoleate column 3, lines 8 and for "halopoxyalkanes" read haloepoxyalkanes column 5,

TABLE I, last column, strike out "Failed l" and insert the same in the next line above, opposite "Ex, 1 (Blank)"; column 6 line '59, for "resinuous" read resinous column 8, l1ne 20 for '"theremoset" read thermoset line 48 for theromet" read thermoset Signed and sealed this 3rd day of September 1963,

(SEAL) Attestz] ERNEST w. SWIDER DAVID LADD Attesting Officer Commissioner of Patents 

1. PLASTICIZED, THERMOST RESINOUS PRODUCT, CONSISTING ESSENTIALLY OF (A) A THERMOSET RESIN FORMED BY REACTION OF A COMPLEX EPOXY RESIN HAVING EPOXY OXYGEN ATTACHED TO ADJACENT CARBON ATOMS ON TERMINAL 3 TO 6 CARBON ALKOXY GROUPS OF THE RESIN ONLY, WITH A CURING AGENT FOR SAID EPOXY RESIN, AND (B) AS AN EXTERNAL PLASTICIZER FOR THE THERMOSET RESIN ABOUT 5 TO 40 PARTS BY WEIGHT OF A GLYCOLETHER ESTER OF THE FOLLOWING FORMULA 